Open Access Research Article the Water Quality of Devoll and Osum

Open Access Research Article

The Water Quality of Devoll and Osum Rivers and Its Impact on the Agricultural Soils

Magdalena Cara 1, Jordan Merkuri 1, Murtezan Ismaili 2, Miranda Huta 3, Bora Qesja 1

1Agricultural University of Tirana, Albania 2South East Europe University 3Centre of Agriculture Technology Transfer, Fushe Kruja

Corresponding author: [email protected] Abstract: The Devoll River, one of the sources of Seman River, joins Osum River in the proximity of Kuçova. The above are both used for irrigation purposes. The studies performed (over a period of four years 2003-2006) were aimed at determining the water quality of the Devoll and Osum rivers together with their impact in agriculture. The maximal sodium values recorded in the Devoll and Osum rivers were 1 mg/L (2003) and 0.66 mg/L (2006) respectively. Magnesium levels ranged from 2.67 mg/L (2003) to 2.96 mg/L (2006) with a 4 year average of 2.79 for the Devoll river and 2.02 mg/L (2006) to 3.55 mg/L (2005) with a 4 year average value of 2.57 mg/L for the - Osum river. The nutritious elements levels were generally low. The average value of N – NO 3 recorded in the + Devoll waters reached 2.02 mg/L, with a maximal value of 5.88 mg/L (2006). The average value of N - NH4 was 3- + calculated to be 1.12 mg/L, while the maximal value reached 2.1 mg/L (2006). PO 4 and K had a maximal value of 0.1 mg/L (2005) and 11 mg/L (2006) respectively. The last value was 5.5 times bigger than the allowed one. - + For the Osum River the maximal values of N - NO 3 and N – NH 4 were 9.02 mg/L (2006) and 3.22 mg/L (2006) 3- + respectively. The maximal values of PO 4 and K were recorded to be 0.228 mg/L (2004) and 12 mg/L (2006). This maximal value is six times bigger than the allowed value. On average nutrient concentrations were higher in 2006 compared to previously recorded values. These concentration levels, with the exception of K +, were however within the FAO standard levels.

Keywords: irrigation, nutrients, parameters, soil, water quality

1.0 Introduction: irrigation purposes and have been a great part of The hydrographical territory of Albania is agricultural and environmental strategies in our approximately 44,000 km 2 or 57% more than the country. national space of our country. The average altitude of this territory is over 700 m above the sea level. The soil and water quality play a prominent role in Rivers have always been the most important the irrigation process. If they were not to be freshwater resources. They find multiple uses in compatible with one another, the watering process agriculture, industry, transportation, aquaculture, might have a negative impact on the physical – public water supply etc. (Ravindra et.al, 2003). The chemical abilities of the soil. The estimation of water multiannual average discharge of Albanian rivers is quality is based on salinity, sodium and toxicity of about 1,245 m 3/s. All the rivers flow in the sea chemical elements (Goel 2006). Salinity is the most direction with about 40 billion m 3 water/year (AKBN, important criterion for evaluating irrigation water 2010). quality (Ghassemi, et al., 1995). High salt concentrations prevent the uptake of water by Devoll and Osum rivers are the main afluents of the plants causing crop–yield reductions. This occurs Seman River. Their watershed areas are 3130 km 2 when salts accumulate in the root zone to such an and 2150 km 2 respectively (Pano, 2008). With their extent that the crop is no longer able to extract geographic positions, both rivers have been used for sufficient water from the salty soil solution, resulting in water stress for a significant period (FAO, 1994).

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Salt concentration can exert an effect or prohibit and 2.1 The Investigated Area delay plant growth. (Rhades, 1977; Raymond et al. , Albania has a mediterranean climate, with a 1995). The irrigation process with low quality water relatively short and soft winter and with a hot and generally does not represent an immediate damage very dry summer. Albania's climate is very different to the plant. However, the damage is inflicted in the depending on the region with contrasts in long run, as the salts or water sodium will be temperature, precipitation, sunshine, air humidity, accumulated in the soil and lowers its productivity. etc. Albania comprises a very concetrated river Regardless of the effects of the hydrochemistry of network. The upper flow has a mountanous the Devoll and Osum Rivers, there are no previous character, is fast and erosive, whereas the lower studies analyzing the physico-chemical parameters, flows have a field character. The Devoll River (196 nutrients, salinity etc. of the water of the two rivers. km) has its sourse at the foundations of the Gramoz Moreover, there exist no evaluations of the effects Mountain. It continues its flow north to the city of the latter can have on the soil and cultivated Bilisht, returning then west through the valley vegetation. The object of the study is to analyze the between the Dry Mountain north and that of water quality of the Devoll and Osum rivers. The aim Morava in the south, where it joins river Osum of the study is to assess their impact on agricultural (which flows too from the Gramoz Mountain). lands and to recommend plants that are more Together they form the Seman River. The water suitable for cultivation. gathering surface of the Devoll River is 3.130 km². The average discharge is around 49.5 m³/s. The 2.0 Materials and Methods: Osum River is 161 km, with a water gathering The Osum and Devoll rivers and the agricultural soils surface of 2.150 km 2, average altitude of 828 m and adjacent to them were monitored for a period of average multiannual discharge of 32.5 m 3/s. Both four years (2003 – 2006). rivers have an important impact on agriculture.

Figure 1. Map of area under investigation Figures 2 and 3. Areas of samples collection

Figure 4. Devoll River, sampling place Figure 5. Devoll River, sampling place

Figure 6. Osum River, sampling place Figure 7. Osum River, sampling place

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2.3 Samples and Analytical Methods The locations used for sampling are located in: Murras – Elbasan, Fushë – Devoll, Devoll – Korçë dhe Berat. The collection of water samples has been done conforming to standard methods ISO 5667 - 3:200. The collection of soil samples has been done [Na +], [Ca 2+ ], dhe [Mg 2+ ] are the concentrations in conforming to standard methods ISO 10381-1993. mmol/L of sodium, calcium dhe magnezium ions in Concerning the measurements, contemporary the soil solution. The Na +, Ca 2+ dhe Mg 2+ ion methods were used: spectrometric and standard concentrations were determined by extracting the classical methods. The determination of the ions from the soil in the solution and using the exchange cation capacity has been done with the Spectroscopy of Atomic Absorption. When SAR employment of the methodics ISO 11260-94. Nitrate, increases over 12 – 15, there are serious physical ammonium, phosphate etc., levels were analyzed problems and furthermore plants show difficulties in according to the standard methods described by the absorption of water. APHA, 1998 & Rodier 1984. Samples for cations (calcium, magnesium) were analyzed by atomic 3.0 Results and Discussion absorbance spectrophotometry, while sodium was The results of the parameters are presented on measured by flame photometry. Bicarbonate level Tables (1 - 7) and Graphics (1 – 9). was determined by the acid titration method while the organic matter was determined by the permanganate oxidation method (Golterman, 1978). 3.1 The pH Measurement The physico-chemical parameters such as pH and For Devoll and Osum Rivers, the analyzed water temperature were measured in the field using a pH samples had pH values of 7.2 – 7.7 and 7.1-7.9 meter while the conductivity of water was measured respectively (Table 1 and 2). Conforming to the FAO by a conductivity meter. specifications, the most adequate pH intervals on irrigation waters are 6.0-8.5, (Ayers et.al. 1976, The soil samples tested were implemented 1885, 1994) whereas conforming to the Irrigation according to ISO 10381-1993 method standard. For water quality criteria pH = 5 - 7 (Bradli 1998, 2000) parameter measures, the contemporary methods of intervals are recommended. determination such as: Spectroscopy of Atomic Absorption method and interfrequently classical 3.2 Electric Conductivity (EC) standard methods of analysis were used. The The average electric conductivity of the water determination of effective cathion exchange, samples collected in the Devoll River in the - capacity and base saturation level was achieved via monitored years 2003-2006 has been 0.48-0.65 dSm 1 -1 the usage of a barium chloride solution ISO 11260-94. while for the Osum river 0.45-0.53 dSm (Table 1 The soil quality sampling was implemented and 2). The salinity tolerance of plants is related to according to ISO 5667 -1-1980. The water samples the salinity of the soil, described as EC. EC is directly were analyzed according to the salt contents, pH, related to the concentration of ions dissolved in the electrical conductivity, kations, anions (Ca 2+ , Mg 2+ , water. All the collected water samples (Figures 3 and + 2- - - 2- Na , CO 3 , HCO 3 , Cl , SO 4 ), nutritious elements 4, Devoll River and Figures 5 and 6, Osum River) - + 3- + (NO 3 , NH 4 , PO 4 , K ), acidity, ratio of sodium were of no salinity, i.e. have no negative effect on absorption, dry residue and heavy metals (Zn, Pb, the agricultural soil and its cultivated plants. Mn, Fe, Cu, Cr). 3.3 The Dry Residue The SAR (Sodium Absorption Ratio) parameter The values of dry residue for the waters of the Devoll evaluates the sodium hazard in relation to calcium River are 0.189 g/L (2005) in 0.508 g/L (2003) with and magnesium concentrations (Richards 1954). SAR an average value of 0.324 g/L and for Osum River are was calculated using the following formula: 0.106 g/L (2005) in 0.316 g/L with an average value of 0.241 g/L, (Table 1 and 2).

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Table 1. Physico-Chemical Parameters of Devoll River in the samples collected during 2003 - 2006.

Parameter s Units Intervals 2003 2004 2005 2006 pH - log [ H+] 6.0 - 8.5 7.2 7.7 7.4 7.5 Conductivity (dS/m) 0 – 3 0.65 0.48 0.52 0.57 (ECW) Dry residue g/l 0.25 0.32 0.11 0.29 SAR m.e/l 0 – 15 0.64 0.39 0.23 0.30

Table 2. Physico-Chemical Parameters of Osum River in the samples collected during 2003 - 2006.

Parameters Units Intervals 2003 200 4 2005 2006 pH - log [ H+] 6.0 - 8.5 7.1 7.9 7.1 7.1 Conductivity (dS/m) 0 – 3 0.47 0.45 0.46 0.53 (ECW) Dry residue gr/l 0.25 0.32 0.11 0.29 SAR m.e/l 0 – 15 0.44 0.39 0.25 0.38

Table 3. Nutrient Levels in the Devoll River Samples 2003 – 2006.

Nutrients Units Intervals 2003 2004 2005 2006 - mg/l 0-10 0.28 0.56 1.34 5.88 N- NO 3 + mg/l 0-5 0.7 0.28 1.4 2.1 N- NH 4 3- mg/l 0-2 0.066 0.074 0.100 0.042 PO 4 + mg/l 0-2 5.42 2.761 1.668 11 K

Table 4. Nutrient Levels in the Osum River Samples 2003 – 2006.

Nutrients Units Intervals 2003 2004 2005 2006 - N- NO mg/l 0-10 0.14 0.56 2.8 9.02 3 + N- NH mg/l 0-5 - 0.28 1.26 3.22 4 3- PO mg/l 0-2 0.108 0.228 0.154 0.015 4 + K mg/l 0-2 2.63 1.881 1.356 12

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Graph 1. Cations in mg/L River Devoll (2003 – 2006)

Graph 2. Cations in mg/L River Osum (2003 – 2006)

3.4 Sodium years duration was 2.77 mg/L. The calcium The sodium values wereas follows: minimal values of concentration in the Osum waters was 1.52 mg/L 0.37 mg/L (2005) in the Devoll River with a maximal (min value, 2004) and 3.99 mg/L (max value, 2006), value of 1 mg/L (2003). In the Osum River the (Graph.2). The average value was 2.44 mg/L. For minimal values were 0.43 mg/L (2005) and the magnezium the concentration in the Devoll river maximal values 0.66 mg/L (2006). High varied from 2.67 mg/L (2003) to 2.96 mg/L (2006) concentration of ions Na + in water is undesirable with a 4 year average of 2.79; for the Osum River it because Na interferes with other ions absorption, varied from 2.02 mg/L (2006) to 3.55 mg/L (2005) destroying the soil structure, closing the soil pores (Graph.2) with a 4 year average value of 2.57 mg/L. and reducing the water flowing (Laze et al., 2002). The values of SAR (Sodium Absorption Ratio) are The medium and high levels of sodium in water shown in tables 1 and 2. They range from 0,23 – 0,64 could become toxic for some sensitive plants (fruit m.e./L for Devoll River and from 0,25 – 0,44 m.e./L trees or ornamental plants). for Osum River. The medium and high levels of calcium and magnezium in water could become toxic 3.5 Calcium and Magnezium for some sensitive plants. The calcium concentration in the Devoll waters was 1.92 mg/L (min value, 2004) and 4.55 mg/L (max 3.6 Anion Concentration value, 2006) (Graph.1). The average value for the 4 The anion levels in water were as follows: the

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sulphate ions concentration in the Devoll river was considered harmful to the growth of plants. Water 0.2 (min values) and 9.79 mg/L (max value) for 2003 with hydrogen carbonates values above 2.5 is not and 2004 respectively. The measured minimal and considered suitable for irrigation purposes, and maximal values are shown Graph 3. In the Osum water with hydrogen carbonates values less than River, the concentrations of the carbonate ions, 1.25 is considered safe. (Yang et.al 2012). Chlorides hidrogen carbonates and chlorine are presented in are important inorganic anions which contain Graph 4. A high value of hydrogen carbonates in varying concentrations in natural waters (Makhoukh water value leads to an increase in the adsorption of et. al 2011). Chlorides are troublesome in irrigation sodium on soil. Irrigation water having hydrogen water and also harmful to aquatic life (Rajkumar carbonates values greater than 5 has been et.al 2004).

Graph. 3. Anions in mg/L River Devoll (2003 – 2006)

Graph 4 . Anions in mg/L River Osum (2003 – 2006)

+ 3.7 Nutritious Elements (Fraser and Chilvers 1981). For N - NH 4 , the average The nutritious element levels are generally low for N value was 1.12 mg/L, the minimal value 0.28 mg/L - NO - in the Devoll waters with the average value (2004) and the maximal value was 2.1 (2006). The 3 3- being 2.02 mg/L. The minimal measured value was average value for PO 4 was 0.071 mg/L, the minimal 0.28 mg/L (2003) and the maximal one was 5.88 value was 0.042 mg/L (2006) and the maximal value - 0.1 mg/L (2005). For K+ the average value was mg/L (2006). All the water samples had higher NO 3 levels, but less than the 10 mg/L limit calculated as N. 5.11mg/L, the minimal value 1.67 mg/L (2005) and Nitrate is an acute contaminant, which means that a the maximal value 11 mg/L (2006). This maximal single exposure can affect the health of people. value is 5.5 times bigger than the allowed value

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(Table 3). For the Osum River, the average value for 3.8 Soil Samples - N - NO 3 was 2.93 mg/L, the minimal measured value The soil texture results are presented in Graph 5, for 0.14 mg/L (2003) and the maximal value was 9.02 the soil adjacent to the Devoll River, and in Graph 8, + mg/L (2006). For N - NH 4 , the average value was for those adjacent to River Osum. It can be noticed 1.57 mg/L, the minimal value 0.28 mg/L (2004) and from the charts, that the texture of these soils is 3- the maximal value was 3.22 (2006). For PO 4 the respectively silty – sandy – clay and silty – clay – average value was 0.126 mg/L, the minimal value sandy. Referring to the conductivity EC (ds/m), 0.015 mg/L (2006) and the maximal value 0.228 Tables 1 and 2, plants that should be cultivated in mg/L (2004). The average value for K+ was 4.47 mg/L, these areas are recommended for salinity ranging the minimal value reached 1.88 mg/L (2004) and the from “low” to “averagely sensitive plants” according maximal value was 12 mg/L (2006). This maximal to Table 8. value is 6 times bigger than the allowed value (Table 4). Nutrients can play a role in toughening up the The heavy metals and microelements in both rivers plant to make it more resistant to dry conditions, have not reached disturbing levels (Graph 6, 7 and 9). disease and wear. For example, sufficient potassium Magnesium, an essential nutrient for plants as well encourages the thickening of cell walls in turf leaves, as for animals, is washed from rocks (dolomite, toughening the plant so it becomes more wear magnesite, etc.) and subsequently ends up in water, resistant (Handreck and Black 2002). With the only being also responsible for water hardness. (Trivedi et. expection of Potasium, the nutrient levels in the al 2009). Such soils tend to have a relatively high pH waters of Osum and Devoll in all samples taken (approximately 7 10), as sodium carbonate is much during 2004 – 2006 result in the status “bad” or – “very bad” conforming to the NIVA classification. more soluble than calcium or magnesium carbonates; (Bratli, 1998 and 2000). As a result, higher concentrations of carbonate and bicarbonate are maintained in sodic soil solutions

(Rengasamy and Olsson 1991, Brady and Weil 1999). Rivers contain approximately 4 mg/L of magnesium and a concentration of 30 and 50 mg/L is recommended for drinking waters in EPA (U.S. EPA) 2002.

Graph 5. Texture analysis of adjacent soil to River Devoll.

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Graph 6. Microelements in the adjacent soils to River Devoll.

Table 5. Monitored parameters in the adjacent soils to River Devoll – Korcë

Samples pH K Humus N P K Ca Mg Na KKK Ppm % ppm m.e/100 gr Soil P 1 6.5 133 2.6 0.133 38.4 0.34 16 6.5 0.74 36.07 P 2 7.9 95 1.9 0.098 32.2 0.24 21.9 2.5 0.73 26.56 P 3 7.2 143 4.5 0.217 45.0 0.37 20.4 5.8 1.25 32.23

Graph 7. Heavy metals in the adjacent soils to River Devoll –Korcë (2003 – 2006) in mg/Kg

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Graph 8. Analysis of the mechanical contents of the adjacent soils to River Osum in 3 points.

Table 6. Monitored parameters in the adjacent soils to River Osum

Samples pH K Humus N P K Ca Mg Na KKK Ppm % Ppm m.e/100 gr So il P 1 8.0 93 1.9 0.176 0.13 0.24 17. 3 3.2 0.13 21.46 P 2 8.3 174 1.2 0.112 0.30 0.44 17. 6 4.7 0.30 24.35 P 3 8.0 280 1.6 0.149 0.26 18.6 3.38 0.72 0.26 27.85

Graph 9 . Microelements in the adjacent soils to River Osum. (2003-2006).

Table 7. General classification of water sodium hazard based on SAR values SAR values Sodium hazard of water Comments 1-9 Low Use on sodium sensitive crops must be cautioned 10 -17 Medium Amendments (such as gypsum) and leaching needed 18 -25 High Generally unsuitable for continuous use ≥26 Very High Generally unsuitable for use

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Table 8. Soil and water salinity criteria based on plant salt tolerance groupings

Plant salt tolerance Water or soil Average root zone s Grouping salinity rating alinity EC (dS/m) Sensitive crops Very low <0.95 Moderately sensitive crops Low 0.95 – 1.9 Moderately tolerant crops Medium 1.9 – 4.5 Tolerant crops High 4.5 – 7.7 Very tolerant crops Very high 7.7 – 12.2 Generally too saline Extreme >12.2

4.0 Conclusion: organic content will tend to decrease the pH because The water quality was assessed with respect to its of the carbonate chemistry. A neutral pH in the suitability for irrigation activities. Based on the results, interval (6.5–8.5) characterizes water where life it can be concluded that the water quality is relatively develops in an optimal way (Bhatt, 1999). According good. Hydrogen carbonate was the dominant anion, to water analysis, the pH has resulted relatively while sodium and calcium were the dominant cations neutral with a very slight tendency basic. in most rivers samples. The main anion differences - Physicochemical parameters were used to evaluate are that in river water HCO 3 has a much higher concentration than Cl - (which has the lowest the quality of river water for determining its concentration out of the major anions in river water). suitability for irrigation purposes. Calculated values of The chemical composition of the river water showed SAR indicate that most of river water is suitable for 2- irrigation of most crops. Systematic monitoring that HCO 3¯ and SO 4 were the most abundant anions while Ca 2+ the most abundant cation. High content of programs are urgently needed in order to understand bicarbonate and calcium in river sites confirm the fact and evaluate the actual state and water quality of that 98% of all river waters was of the calcium these rivers and also to determine the main pollution carbonate type (Ramesh, R. 1989). Calcium, sources and the irrigation potential (Cuena 1989). Magnesium and Bicarbonate are contributed to river water mostly by rock weathering. Calcium is the main References: cation in river water, followed by Mg and Na, then K. 1) Agjencia Kombëtare e Burimeve Natyrore Water chemistry of the rivers can reflect changes in (AKBN), Burimet Hidroenergjetike. (2010). f. 239 their watersheds, making rivers good indicators of dhe 244. land use (Meybeck and Helmer 1989). According to 2) APHA, (1998) Standard Methods for the Examination the Richards (1954), the low to medium SAR of rivers of Water and Wastewater, American Public Health makes it suitable for irrigation of most crops with Association, Washington, DC, USA, 18th edition. little danger of development of exchangeable sodium 3) Ayers, R.S. & D.W. Westcott. (1976). Water and salinity, although few of hard water can have high Quality for Agriculture. Irrigation and Drainage EC in the Devoll and Osum River. Referring to Paper No. 29. Food and Agriculture Organization different guides and standards of FAO, EU and the of the United Nations. Rome. p. 89-92. U.S., not only the physical/chemical water conditions 4) Ayers, R.S., Westcott, D.W., (1985). Water Quality and their impact on land were determined, but also for Agriculture. FAO Irrigation and Drainage the required plants that can be grown in those Paper 29 rev. 1, Rome, 174 pp. characteristiced soils ca be recommended. Analysis 5) Ayers, et.al. (1994). Guidelines for interpretation performed (texture) in our land have shown a of irrigation water quality problem. (R.S. FAO relatively light silt-sand soil (Hameed et.al. 1966). In irrigation and drainage paper, 1994) general these soils have deficiency in nourishing 6) Bhatt L. R., Lacoul P., Lekhak H. D., and Jha P. K., elements. Sulfate in water exists as negatively (1999) “Physico-chemical characteristics and charged ions. It contributes to the total salt contents. phytoplanktons of Taudaha lake, Kathmandu” The principal component regulating ion pH in natural Pollution Research, vol. 18, no. 4, pp. 353–358. waters is the carbonate, which comprises CO 2, H 2CO 3 7) Brady NC, Weil RR (1999) ‘The Nature and Properties (Larpent, 1997). Low values in pH are indicative of of Soils.’ (Prentice Hall: Upper Saddle River, New high acidity, which can be caused by the deposition of Jersey). acid forming substances in precipitation. A high

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